CN113764202A - Preparation method of supercapacitor electrode on film based on mixed cellulose ester - Google Patents
Preparation method of supercapacitor electrode on film based on mixed cellulose ester Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of a supercapacitor electrode based on a mixed cellulose ester film, which is characterized in that an electrode material and the mixed cellulose ester film are firmly and tightly combined together by utilizing negative pressure generated in the suction filtration process to prepare the electrode. The mixed cellulose ester film effectively realizes the three-in-one function of 'filter membrane, electrode and diaphragm', not only serves as a pumping filter membrane, but also serves as a flexible substrate of an electrode material, and can also serve as a 'diaphragm', so that an additional diaphragm material is not needed when the mixed cellulose ester film is assembled into a super capacitor device or applied to a test. The invention breaks the limitation that conductive metal is frequently selected as the current collector at present, omits the complicated preparation process of the electrode and the current collector and greatly simplifies the preparation process of the electrode.
Description
Technical Field
The invention belongs to the field of electrochemistry, relates to an electrode material applied to a super capacitor, and particularly relates to a preparation method of a super capacitor electrode based on a mixed cellulose ester film.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a storage battery, has higher electrostatic capacity compared with the traditional capacitor, has the characteristics of high power density, high charging and discharging speed, long cycle life, environmental protection and the like compared with a lithium ion battery and a fuel cell, and has wide application prospect in the fields of electric automobiles, mobile communication, military, industry and the like.
At present, a super capacitor is generally mainly composed of 4 parts such as an electrode, a current collector, an electrolyte, a diaphragm and the like, and electrode materials applied to the super capacitor at present mainly comprise carbon-based materials, metal oxides, hydrate materials and conductive polymer materials, active substances of the electrode materials mostly exist in the form of powder, and the current collector is required to be used as a carrier for supporting. The combination mode and preparation process of the active material and the current collector greatly influence the electrochemical performance of the electrode. The conventional preparation process of the current electrode material active substance and the current collector adopts a conductive agent, a binder and the electrode active substance which are mixed according to a certain proportion to prepare electrode slurry, and then the electrode slurry is coated or manually titrated on carbon cloth (the current collector), the use of the conductive agent and the binder affects the electrochemical performance of the electrode material, and particularly the use of the binder reduces the electrochemical performance of the electrode material. In addition, the process has higher requirements on the process technique of an operator, and instability and uncertainty factors are brought to the electrochemical performance test of the electrode. In order to make the current collector contact with the active material sufficiently, the internal resistance is as small as possible, and the choice of the current collector is often limited to conductive metals with higher cost, such as copper, aluminum, and the like.
In recent years, a novel two-dimensional layered material MXene (general formula M)n+1XnTx) The material is a star material for energy storage due to good conductivity, abundant surface functional groups, good hydrophilicity, high volume specific capacity and high cycling stability. The composite membrane can be stripped into a single-layer or few-layer nanosheet by physical ultrasound or intercalation, a nanosheet solution can be self-assembled into a membrane by vacuum filtration of a mixed cellulose ester membrane (a pumping membrane), a self-supporting flexible membrane can be stripped from the mixed cellulose ester membrane (the pumping membrane) after vacuum drying to be directly used as an electrode, and a current collector is not needed any more. For the film-forming material directly used as an electrode, the current process idea is to separate an electrode film from a suction filtration film. The MXene nano-sheet has a certain massThe MXene material can be separated from the suction filtration membrane, but the problems of low concentration and low yield of the MXene material exist, so that the preparation of the MXene material in a large-area membrane forming process is limited and the difficulty of the MXene material stripping process is caused. And the toughness of the membrane is not good, so that the membrane is easily damaged in the membrane stripping process, and the large-scale production and industrialization of the membrane electrode are not facilitated.
In addition, when the components such as the mutually independent electrodes, the diaphragms and the like in the super capacitor are stacked and assembled layer by layer, the relative displacement or separation of the adjacent components is easy to occur under the deformation, and the continuous and effective transmission of stress or current carriers is not facilitated. Sometimes, the electrode and the diaphragm are not in good contact, so that assembly failure is easily caused, and waste of electrode materials and diaphragm materials is caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the preparation method of the supercapacitor electrode based on the mixed cellulose ester film, which is simple to operate and wide in adaptability, the preparation process of the electrode is greatly simplified, and the prepared electrode has excellent electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a supercapacitor electrode based on a mixed cellulose ester film comprises the steps of uniformly dispersing an electrode material into deionized water to prepare a low-concentration electrode solution, configuring the concentration of the electrode solution according to the requirement that the electrode material is attached to the mixed cellulose ester film and does not break away from the mixed cellulose ester film, uniformly distributing the electrode solution on the mixed cellulose ester film in a vacuum filtration mode, and drying in a vacuum oven to prepare the flexible electrode.
Further, the electrode material is a carbon material, an MXene material, a conductive polymer, a metal powder, a metal oxide, a metal hydroxide, an oxyhydroxide, or an oxyhydroxide.
Further, the carbon material is a carbon nano tube or graphene, the MXene material is vanadium carbide or titanium carbide, the conductive polymer is polyaniline, polypyrrole or polythiophene, the metal powder is manganese powder, iron powder, copper powder or zinc powder, the metal oxide is vanadium oxide, manganese oxide or cobalt oxide, the metal hydroxide is cobalt hydroxide or nickel hydroxide, the hydroxyl oxide is iron oxyhydroxide, cobalt oxyhydroxide or nickel oxyhydroxide, and the metal acid salt is vanadate, manganate or titanate.
Further, the electrode material is uniformly dispersed into deionized water by adopting an ultrasonic dispersion method, a magnetic stirring method, a mechanical stirring method or a rapid mixing method to prepare a low-concentration electrode solution.
Further, the mixed cellulose ester film is an aqueous film or an organic film.
Further, the mixed cellulose ester membrane pore sizes include 0.22, 0.45, 0.8, 1.2, and 2.0 μm.
The preparation method of the supercapacitor electrode based on the mixed cellulose ester film has the advantages that:
1. the invention provides a preparation method of a supercapacitor electrode based on a mixed cellulose ester film, which is characterized in that a small amount of low-concentration electrode material solution is filtered on the mixed cellulose ester film, and the electrode material and the mixed cellulose ester film are firmly and tightly combined together by using negative pressure generated in the filtering process to prepare the electrode. The mixed cellulose ester film is a non-conductive film material with a certain pore diameter, and the mixed cellulose ester film not only serves as a suction filtration film, but also serves as a flexible substrate of an electrode material, so that an ion channel is provided when the mixed cellulose ester film serves as the substrate, and the tight combination mode of the mixed cellulose ester film shortens the transmission path of ions, greatly reduces the ohmic internal resistance of the electrode in practical application, and is beneficial to the electrode material to show more excellent electrochemical performance.
In addition, the non-conductive nature of the mixed cellulose ester film allows the other side of the film to act as a "separator", eliminating the need for additional separator material when assembled into a supercapacitor device or when used in testing. The mixed cellulose ester film is used as a filtration membrane, a flexible substrate of an electrode material and a diaphragm, so that the use of the diaphragm material is saved, the stability of the electrode structure is effectively improved, the inconvenience of using conductive metal as a current collector in multiple choices at present is broken, the complicated preparation process of the electrode and the current collector is omitted, and the preparation process of the electrode is greatly simplified. The method also avoids the membrane stripping process of MXene materials, can finish the electrochemical performance test of the electrode with a small amount, reduces the influence caused by yield problems, and is expected to realize large-scale production.
2. The invention provides a preparation method of a supercapacitor electrode based on a mixed cellulose ester film, wherein the mixed cellulose ester film is a filter film and has low cost, the prepared electrode has a three-purpose effect of 'filter film, electrode and diaphragm', the single function that the mixed cellulose ester film is only used as the filter film or a flexible substrate at present is broken through, the preparation method is different from the technology that the electrode is prepared by using a diaphragm material through suction filtration and is easy to cause circuit short circuit, the three-in-one effect of 'filter film, electrode and diaphragm' is effectively realized, and the preparation method is successfully applied to device assembly and test. The three-in-one function can also effectively increase the stability of the electrode structure, reduce the ohmic internal resistance of the electrode in practical application and obtain the electrode with excellent electrochemical performance.
3. The preparation method of the supercapacitor electrode based on the mixed cellulose ester film is particularly suitable for MXene materials with two-dimensional nano flaky structures, and has the characteristic of self-assembly film forming. As long as a small amount of low-concentration MXene nanosheet solution is extracted from the mixed cellulose ester film, a small number of MXene nanosheets are self-assembled to form a film on the surface of the mixed cellulose ester film, most of water molecules in the solution are filtered out through the mixed cellulose ester film with a certain aperture, and part of the MXene nanosheet solution penetrates into the shallow surface of the aperture and is mutually and tightly connected with the mixed cellulose ester film under the action of negative pressure in the suction filtration process to form a stable electrode structure, so that the electrode with excellent film-forming property and flexibility is prepared. The MXene membrane electrode prepared by a small amount of low-concentration materials can effectively avoid the problem that a large amount of MXene nanosheets are easy to re-stack, and is more beneficial to the MXene materials to exert excellent electrochemical performance to the maximum extent, such as specific examples 1, 2 and 3. Meanwhile, due to the special effect of three purposes of 'filter membrane, electrode and diaphragm' of the mixed cellulose ester membrane, the membrane stripping process of the MXene electrode is avoided, the problem that the membrane stripping process is difficult is solved, the problems that the MXene material is difficult to apply due to low concentration and low yield are solved, and the technical scheme is provided for realizing large-scale industrialization of the MXene material. 4. The preparation method of the supercapacitor electrode based on the mixed cellulose ester film, which is provided by the invention, particularly aims at the electrode material in a powder state, gets rid of the traditional and complicated coating process for preparing the electrode, and can avoid using a binder (the use of the binder is not beneficial to the electrochemical performance of the electrode). The adopted suction filtration technology is simple to operate, can ensure that the electrode material prepared on the basis of the mixed cellulose ester film has uniform thickness and has the characteristics of high toughness and high mechanical strength. And the test electrodes showed excellent electrochemical performance as in example 4
5. The invention can be widely applied to various electrode materials, and only a small amount of low-concentration electrode materials can be uniformly dispersed in deionized water. Such as carbon materials, MXene materials, metal powders, conductive polymers, metal oxides, metal hydroxides, oxyhydroxides, or metal acid salts, and the like.
6. The invention provides a guide and innovation of thought, the method for preparing the electrode is different from the method for preparing the electrode by using a diaphragm material through suction filtration, and is also different from the method for preparing the electrode by only using a cellulose ester film as an electrode or a flexible substrate, but the three-purpose preparation effect of 'filter film, electrode and diaphragm' is not realized. The mixed cellulose ester membrane filter membrane is used, the 'three-in-one' effect of 'filter membrane, electrode and diaphragm' is realized, the electrode is successfully prepared, the limitation of material use in electrode preparation is broken through, the mixed cellulose ester membrane filter membrane can only be concentrated in the use of current collector material and diaphragm material and the traditional super capacitor structure, materials with more types and more effects can be applied to flexible energy storage devices such as super capacitors, mixed ion capacitors and secondary batteries, and the mixed cellulose ester membrane filter membrane has wide application prospects in the fields of flexible wearable electronic devices, communication technologies, green energy sources and the like.
Drawings
FIG. 1 is a plot of cyclic voltammograms at different scan rates for supercapacitor electrodes based on mixed cellulose ester films prepared in example 1 of the present invention.
FIG. 2 is a graph showing the charge and discharge curves of the supercapacitor electrode on the mixed cellulose ester film prepared in example 1 of the present invention at different current densities.
FIG. 3 is a graph showing the specific capacity change of supercapacitor electrodes based on mixed cellulose ester films prepared according to example 1 of the present invention at different sweep rates.
FIG. 4 is a plot of cyclic voltammograms at different scan rates for supercapacitor electrodes on mixed cellulose ester films prepared in example 4 of the present invention.
FIG. 5 is a graph showing the charge and discharge curves of the supercapacitor electrode on the mixed cellulose ester film prepared in example 4 of the present invention at different current densities.
Detailed Description
The present invention will be explained in further detail with reference to examples.
In this example, the electrochemical performance of the prepared supercapacitor electrode on the mixed cellulose ester film was completed in a three-electrode system. 3M H is selected2SO4As electrolyte, Hg/Hg2SO4As a reference electrode, activated carbon was used as a counter electrode.
In this example, when the prepared supercapacitor electrode based on the mixed cellulose ester film is subjected to cyclic voltammetry, the electrode is respectively 2, 5, 10, 20, 50, 100, 200mV s-1Cyclic voltammetry tests were performed at different sweep speeds.
In the embodiment, when the prepared supercapacitor electrode on the mixed cellulose ester film is used for carrying out charge and discharge tests, the electrodes are respectively 1, 2, 5, 10, 20 and 50A g-1And carrying out charge and discharge tests under different current densities.
Preparation of a working electrode: pouring the prepared low-concentration electrode solution into a suction filtration device with a mixed cellulose ester film for vacuum filtration. And finally, punching the dried electrode film into a small film with the phi of 0.54mm by using a punching machine to finish the preparation of the working electrode.
Preparing a counter electrode: mixing 95 wt% of activated carbon (YP-50F) and 5 wt% of Polytetrafluoroethylene (PTFE) binder, and adding a proper amount of ethanol solution to prepare mixed slurry. And then continuously grinding until the film is clay-shaped, rolling the clay-shaped film on a glass plate by using a glass rod to form a whole film, and finally beating the dried activated carbon film into a small film with the phi of 0.54mm by using a punching machine. And finishing the preparation of the counter electrode.
Example 1
Taking a single or few layers of V4C3Tx(MXene) nanosheet suspension 5mL (0.2mg mL)-1) Pouring the mixture into 20mL of deionized water, uniformly mixing, pouring the mixture into a suction filtration device with a mixed cellulose ester membrane for vacuum filtration, and then placing the membrane electrode after the vacuum filtration in a vacuum oven for drying at 60 ℃. And finally, punching the dried electrode film into a small film with phi 0.54mm by using a punching machine.
For the electrochemical performance test of the supercapacitor electrode on the mixed cellulose ester film according to the embodiment, fig. 1 is a cyclic voltammetry curve of the film electrode at different sweep rates, fig. 2 is a charging and discharging curve of the film electrode at different current densities, and fig. 3 is a specific capacity change curve of the film electrode at different sweep rates. As can be seen from the test results of FIGS. 1 and 2, the electrochemical performance of the electrode material test is good, V4C3Tx(MXene) has a pair of redox peaks on a cyclic voltammetry test curve, the tested curve does not deform even at a high scanning speed, and the curve is in a triangle shape with good symmetry in a charge-discharge test, which shows that the prepared electrode has good reversibility. As can be seen from the test results in FIG. 3, the electrode was at 2mV s-1The lower part can reach 307.0F g-1Even at 200mV s-1Still 240.6F g at high sweeping speeds-1The electrochemical material shows excellent rate performance (78.4%), does not cause short circuit phenomenon under the condition of not using an additional diaphragm material, and also successfully tests stable and good electrochemical performance, and the electrode of the electrochemical material is flexible and is not easy to break.
Example 2
Example 1 was repeated with the difference that:
taking Mo in single-layer or few-layer2TiC2Tx(MXene) nanosheet suspension 2mL(0.5mg mL-1) And pouring the mixture into 20mL of deionized water, and uniformly mixing to prepare the low-concentration electrode solution.
Example 3
Example 1 was repeated with the difference that:
taking single or few Ti layers3C2Tx(MXene) nanosheet suspension 1mL (1mg mL)-1) And pouring the mixture into 20mL of deionized water, and uniformly mixing to prepare the low-concentration electrode solution.
Example 4
Example 1 was repeated with the difference that:
taking 1mg of molybdenum trioxide powder, pouring the molybdenum trioxide powder into 20mL of deionized water, and uniformly mixing to prepare a low-concentration electrode solution.
Electrochemical performance of the supercapacitor electrode based on the mixed cellulose ester film of the embodiment is tested, fig. 4 is a cyclic voltammetry curve graph of the film electrode at different sweep rates, and fig. 5 is a charge-discharge curve graph of the film electrode at different current densities. Two pairs of oxidation-reduction peaks can be clearly seen from the cyclic voltammetry test chart, and an obvious platform appears in a charge-discharge curve, which indicates that the electrode material is a battery-type capacitor material and is 2mV s-1Then reaches 191.8F g-1The electrode prepared on the basis of the mixed cellulose ester film truly reflects the electrochemical performance of the electrode material.
Claims (6)
1. A preparation method of a supercapacitor electrode based on a mixed cellulose ester film is characterized by comprising the following steps: uniformly dispersing an electrode material into deionized water to prepare a low-concentration electrode solution, configuring the concentration of the electrode solution according to the requirement that the electrode material is attached to the mixed cellulose ester film and does not break away from the mixed cellulose ester film, uniformly distributing the electrode solution on the mixed cellulose ester film by using a vacuum filtration mode, and drying in a vacuum oven to prepare the flexible electrode.
2. The method of claim 1 for making a supercapacitor electrode on mixed cellulose ester film based, wherein: the electrode material is carbon material, MXene material, conductive polymer, metal powder, metal oxide, metal hydroxide, oxyhydroxide or oxyhydroxide.
3. The method of claim 2 for making a supercapacitor electrode on mixed cellulose ester film based, wherein: the carbon material is a carbon nano tube or graphene, the MXene material is vanadium carbide or titanium carbide, the conductive polymer is polyaniline, polypyrrole or polythiophene, the metal powder is manganese powder, iron powder, copper powder or zinc powder, the metal oxide is vanadium oxide, manganese oxide or cobalt oxide, the metal hydroxide is cobalt hydroxide or nickel hydroxide, the hydroxyl oxide is ferric hydroxide, cobalt hydroxide or nickel hydroxide, and the metal acid salt is vanadate, manganate or titanate.
4. The method of claim 1 for making a supercapacitor electrode on mixed cellulose ester film based, wherein: the electrode material is uniformly dispersed into deionized water by adopting an ultrasonic dispersion method, a magnetic stirring method, a mechanical stirring method or a rapid mixing method to prepare a low-concentration electrode solution.
5. The method of claim 1 for making a supercapacitor electrode on mixed cellulose ester film based, wherein: the mixed cellulose ester film is an aqueous film or an organic film.
6. The method of claim 1 for making a supercapacitor electrode on mixed cellulose ester film based, wherein: the mixed cellulose ester membrane pore sizes include 0.22, 0.45, 0.8, 1.2, and 2.0 μm.
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